DE3730781C2 - - Google Patents

Description

The invention relates to water-in-oil dispersions of cationic, crosslinked polymers and use of water-in-oil dispersions of cationic, ver wet polymers to thicken water and aq solutions and for the production of printing pastes for textile printing.

Polymers dissolved in water or aqueous salt solutions show thickening properties and a viscosity increase due to the presence of water swellable Particles are used in many areas of the Technique, cosmetics or pharmacy used. The natural occurring substances, such as alginates, guar gum or Starch (ester / aether) are increasingly going through replaced synthetic polymers, among others Polymers of acrylic compounds are used.

In this case, by installing multi-functional connec three-dimensional networks of such high molecular weight weight created that the products only water are swellable. However, it can still be water soluble Liche shares be present.

In particular, water-in-oil emulsion polymers the These acrylic compounds prepared by polymerization in "reverse phase", offer because of their light weight Recoverability in water benefits. The manufacturer development of water-soluble polymers of this substance By emulsion polymerization is in the US-PS 32 84 393 and described in DE-OS 22 26 143 ben. The addition of the reverse emulsifier is carried out according to DE-OS 22 26 143 by adding to the aqueous phase. To DE-OS 24 31 794, the Umkehremulgator also in the emulsion already be incorporated (selbstin inverting emulsion). Crosslinked, water-insoluble or water-swellable polymers from the acrylic series with water-soluble fractions for nonionic or anionic Icelandic monomers are z. B. in GB-PS 20 07 238 and described in US-PS 45 54 018.

Water-soluble, non-crosslinked emulsion polymers from the acrylic series with cationic monomers described in DE-OS 27 56 697, their preparation and application, however, on their particular one sentence purpose (flocculant) are tailored. When Thickeners for non-aqueous solutions are used in the EP Application 01 96 162 weakly crosslinked emulsion poly merisate with cationic (meth) acrylic esters mentioned.

Corresponding cationic, crosslinked polymers of substituted (meth) acrylamides in emulsion form are new. They can be surprisingly with you produce very good thickening effect.

The invention relates to water-in-oil Disper water-swellable, cross-linked, cationic Polymers consisting of

• A) from 30 to 70% by weight of homopolymers or copolymers,
• B) 20 to 50 wt .-% of a water-immiscible organic liquid,
• C) 0.5 to 10% by weight of a water-in-oil emulsifier,
• D) optionally 0.5 to 10% by weight of a wetting agent,
• E) balance to 100% by weight of water,

which are characterized in that the homo- or Copolymers by polymerization

• a) 50 to 99.99% by weight of a monomer of the general formula: in the
  R₁ = hydrogen or methyl,
  R₂ and R₃ are hydrogen or alkyl radical having 1 to 4 carbon atoms,
  R₄ and R₅ are alkyl radicals having 1 to 4 carbon atoms,
  X = -NH- and
  n = a number from 0 to 1,
  as salt or in quaternized form,
• b) 0 to 49.99% by weight of comonomers of (meth) acryl amide, (meth) acrylic acid, (meth) acrylamidomethylbutane acid and / or acrylamidomethylpropanesulfonic acid and / or their salts,
• c) from 0.01 to 5% by weight of polyfunctional compounds as a crosslinker

are available.

Examples of cationic monomers are: Dimethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃ = H; R₄, R₅ = CH₃) and tetra methylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃, R₄, R₅ = CH₃) and salts thereof and quaternary compounds. The amide derivatives are particularly advantageous because it is because of the carboxylic acid amide group when used in aqueous solution meaning tend to be more hydrolysis resistant than the (meth) acrylic säureester. The amide group is also more hydrophilic as the ester grouping and "reinforced" on this Way the water swellability.

As salts, the reaction products come with strong or weak acids, preferably with salt or Sulfuric acid in question. For quaternization is before preferably methyl chloride, sodium chloroacetate, dimethyl sulfate or dimethyl carbonate used.

If the cationic, crosslinked polymers are not are prepared as homopolymer, should be in Copoly at least 50% by weight, preferably 80% by weight cationic polymer.

Comonomers are preferably (meth) acrylamide, (Meth) acrylic acid and acrylamidomethylpropanesulfone acid and / or the salts of these acids in question.

As the oil phase of the W / O emulsion do not come with water miscible hydrocarbons into consideration, for. B. aroma tables liquid hydrocarbons, such as toluene and Xylene, aliphatic liquid hydrocarbons, such as Paraffin oils and saturated hydrocarbons, their Boiling point at a pressure of 1013 hPa in the range from 120 to 350 ° C. One can pure aliphatic Hydrocarbons or mixtures of two or several saturated aliphatic hydrocarbons use. The saturated hydrocarbons are n- and / or i-paraffins. Likewise leave to use oils of natural origin, which Have the advantage of easy biodegradability. Chlorinated hydrocarbons are also suitable as the oil phase such as perchlorethylene, tetrachlorethylene and carbon tetrachloride. The proportion of the oil phase at the total emulsion is 20 to 50 wt .-%.

The technique of polymerization with forming the emul sion, homogenization of the same and release of the Polymerization is known. It is preferably done adiabatic, but just as isothermic at room tempe or at elevated temperature. To Termination of the polymerization, the emulsion in known manner offset with the reverse emulsifier later, the light distribution in the aqueous phase causes. At this time, too a possible post-crosslinking be made.

Crosslinkers are polyunsaturated vinyl, Acrylic or allyl compounds as well as compounds with used several epoxy groups. For networking during the polymerization, methylene bis acrylamide and quaternary compounds of triallyl amines, in particular tetraallyl or triallylmethyl ammonium chloride, but also Allylglycidylaether, Ethy glycol diglycidyl ether, glycerol triglycidyl ether and glycidyl (meth) acrylate as suitable. For one Crosslinking after the actual polymerization kom preferably the epoxy compounds in question. The Connections are both single and in Kombina tion can be used.

When introducing the dispersion of the invention crosslinked, cationic polymers enters water virtually immediate distribution with high thickening of the medium, so that no elaborate Rührvorrich etc. are necessary, which is a considerable advantage tet. Thus, the dispersions provide effective Ver Thickener for aqueous solutions, which in speci ellen application areas where the presence cationic groups of importance is to bear come.

The invention further relates to the use of water-in-oil dispersions of water-swellable, crosslinked, cationic polymers consisting of

• A) from 30 to 70% by weight of homopolymers or copolymers,
• B) 20 to 50 wt .-% of a water-immiscible organic liquid,
• C) 0.5 to 10% by weight of a water-in-oil emulsifier,
• D) optionally 0.5 to 10% by weight of a wetting agent,
• E) balance to 100% by weight of water,

where the homo- or copolymers by polymerization out

• a) 50 to 99.99% by weight of a monomer of the general formula: in the
  R₁ = hydrogen or methyl,
  R₂ and R₃ are hydrogen or alkyl radical having 1 to 4 carbon atoms,
  R₄ and R₅ are alkyl radicals having 1 to 4 carbon atoms,
  X = -NH- or -O- and
  n = a number from 0 to 1,
  as salt or in quaternized form,
• b) 0 to 49.99% by weight of comonomers of (meth) acryl amide, (meth) acrylic acid, (meth) acrylamidomethylbutane acid and / or acrylamidomethylpropanesulfonic acid and / or their salts,
• c) from 0.01 to 5% by weight of polyfunctional compounds as a crosslinker

are available for the production of printing pastes for the textile printing.

The starting monomers are now once the already mentioned cationic (meth) acrylamide derivatives but also the cationic one (Meth) acrylate. Thus, dimethylamines can be noaethyl (meth) acrylamide (R₁ = H, CH₃; X = -O-; n = 0; R₂, R₃ = H; R₄, R₅ = CH₃) and tetramethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -O-; n = 0; R₂, R₃, R₄, R₅ = CH₃) also use.

The novel polymers can hitherto used in cationic textile printing Benzinemul replace so that the so far in the printing process unavoidable hydrocarbon emissions in the Air can be avoided.

The invention is illustrated by the following examples explained in more detail.

used abbreviations -DMAEA = D i m ethylªmino ae thylªcrylat DMAEMA = D i m ethylªmino ae m thyl ethªcrylat DIMAPA Dim = ethylªmino p ropylªcrylamid TEMAPA = Te tra m ethylªmino p ropylªcrylamid TAAC = T etraªllylªmmonium c hlorid TAMAC = T riªllyl m ethylªmmonium c hlorid ABAH = A ZO b is- (2-ªmidinopropan- ydrochlorid h) EO = A o ethylene oxide

Example 1 Dispersion of 80% by weight of DMAEA.CH₃Cl and 20% by weight of acrylamide with 40% by weight of active substance (wS)

Dissolve 640 g of DMAEA · CH₃Cl and 160 g of acrylamide 600 g of water and add 0.5 ml of thioglycolic acid, 0.5 g Trilon® B, 2.5 g TAMAC and 0.6 g ABAH. Man poses adjust the pH to 5.0 with phosphoric acid and pour the solution with stirring in a solution of 40 g sorbi tanmonoisostearate in 480 g isohexadecane. After training that of the pre-emulsion comes with a common household Mixing rod homogenized (viscosity of the emulsion 2500 mPA · s, measured at 20 ° C with Brookfield RVT MK 2/5) and the emulsion by blowing nitrogen under Stirring made free of oxygen. The reaction is isolated with styrofoam and starts at 20 ° C the Polymerization by addition of 4 mg of tert-butylhydro peroxide and 8 mg sulfur dioxide. After 30 minutes is the Peak temperature of 88 ° C reached. It is allowed 1 h stir and mixed with 40 g of nonylphenol-6-AeO and 20 g of nonylphenol-9-AeO. This gives a yellowish opaque emulsion with a viscosity of 3500 mPa · s (Brookfield RVT 2/5, 20 ° C).

With the help of a high-speed stirrer 27.5 g of this emulsion in 1 liter of water containing 0.8 g sodium sulph fat contains, with a milky Form solution that thickens almost immediately. After 5 minutes Stirring the following viscosities are measured (Brookfield RVT, MK 4, 20 ° C):

Speed 1/73 000 mPa · s, 2.5 / 35,000 mPa · s, 4/5 20,000 mPa · s.

example 2 Dispersion of 91.5 wt .-% DMAEA · CH₃Cl and 8.5 wt .-% acrylamide with 47 wt .-% wS

Dissolve 858 g of DMAEA · CH₃Cl and 80 g of acrylamide 470 g of water and add 0.5 ml of thioglycolic acid, 0.5 g  Trilon® B, 2.5 g TAMAC and 0.6 g ABAH. With salt acid is adjusted to pH = 5.0, and you pour the Solution with stirring in a solution of 40 g sorbi tanmonoisostearate in 480 g isohexadecane. After off form the pre-emulsion is homogenized, with a Viscosity of 2500 mPA · s is measured. By one blowing of nitrogen, the oxygen is released from the Emulsion removed and the polymerization by adding of 4 mg of tert-butyl hydroperoxide and 8 mg of sulfur dioxide oxide triggered. After 20 minutes is a Spitzenentempera reached 90 ° C, after 60 min. Stirring is abge cool and activated as in Example 1. The solution in 0.8 wt .-% sodium sulfate solution thickened practically immediately and has the following viscosities (Brook field RVT, MK 4, 20 ° C):

1/98 000 mPa · s; 2.5 / 46,000 mPa · s; 5/26 200 mPa · s.

example 3 Dispersion of 91 wt .-% DMAEA · CH₃Cl and 9 wt .-% acrylic acid with 47 wt .-% wS

Dissolve 858 g of DMAEA · CH₃Cl and 81 g of acrylic acid in 470 g of water and add 0.5 ml of thioglycolic acid, 0.5 g Trilon® B, 2.5 g of TAMAC and 0.6 g of ABAH, where receives a pH of 5.7. You pour this solution while stirring in a solution of 40 g of sorbitan mono isostearate in 480 g isohexadecane. After training the Pre-emulsion and homogenization gives a Visko of 1560 mPA · s at 20 ° C. By blowing in Nitrogen is the oxygen from the emulsion ent removed and the polymerization by addition of 3 mg tert-butyl hydroperoxide and 6 mg sulfur dioxide ge starts. After 30 minutes is a peak temperature of 92 ° C, after 60 min. Stirring is cooled and activated as in example 1.

In addition to virtually immediate thickening has a Solution of 27.5 g of emulsion polymer in 1 liter of 0.8 wt .-% sodium sulfate solution at 20 ° C following Viscosities on:

1/86 000 mPa · s; 2.5 / 39,000 mPa.s; 5/22 000 mPa · s.

example 4 Dispersion of 100 wt .-% DMAEA · CH₃Cl and 54 wt .-% wS

Dissolve 1076 g of DMAEA · CH₃Cl in 340 g of water and Add 0.5 ml of thioglycolic acid, 0.5 g of Trilon® B, 2.5 g TAMAC and 0.6 g of ABAH, after which the pH was adjusted with Hydrochloric acid to 5.0. The formation of the emulsion carried out as in Example 1 (viscosity at 20 ° C: 1840 mPa · s). It is with 6 mg of tert-butyl hydroperoxide and 12 mg sulfur dioxide triggered the polymerization, wherein within 30 min. 95 ° C peak temperature be achieved. After another 60 minutes, you cool off and activated as in Example 1.

Obtained under the same conditions as in Example 1 one in aqueous solution next to virtually immediate Thickening following viscosities:

1/89 000 mPa · s; 2.5 / 42,000 mPa · s; 5/25 000 mPa · s.

example 5 Dispersion of 92 wt .-% DMAEMA · CH₃Cl and 8 wt .-% acrylamide with 50 wt .-% wS

Dissolve 920 g of DMAEMA · CH₃Cl and 80 g of acrylamide 400 g of water and add 0.5 ml of thioglycolic acid, 0.5 g Trilon® B, 2.5 g TAMAC and 0.6 g ABAH. The pH is adjusted to 6.4 with hydrochloric acid. The education the emulsion is carried out as in Example 1 (viscosity: 1400 mPa · s at 20 ° C). It is with 6 mg tert-butylhy droperoxid and 12 mg sulfur dioxide catalyzes wherein within 150 min. 72 ° C peak temperature he be enough. After stirring for 60 minutes, it is cooled. 27.5 g of this emulsion are added with the addition of 2.7 g Nonylphenol-9-AeO in 1 liter of 0.8% by weight sodium introduced sulfate solution, the solution is practical immediately thickened and at 20 ° C the following viscosities having:

1/43 000 mPa · s; 2.5 / 24,000 mPa · s; 5/15 000 mPa · s.

example 6 Dispersion of 81 wt .-% DIMAPA · CH₃Cl and 19 wt .-% acrylamide with 42 wt .-% wS

Dissolve 341.5 g of DIMAPA · CH₃Cl and 80 g of acrylamide 270 g of water and add 0.5 ml of thioglycolic acid, 0.25 g Trilon® B, 1.25 g TAMAC and 0.3 g ABAH. Man poses adjust the pH to 5.0 with hydrochloric acid and pour the Solution with stirring in a solution of 20 g of sorbitan monoisostearate in 240 g isohexadecane. After Homogeni to a viscosity of 3200 mPa · s at 20 ° C. is the injection of nitrogen, the oxygen away. The polymerization is started with 3 mg tert-butyl hydroperoxide and 6 mg sulfur dioxide. To 60 min., A peak temperature of 88 ° C is reached. It is stirred for 1 hour, cooled and activated with 20 g of nonylphenol-6-AeO and 10 g of nonylphenol-9-AeO. The test in 0.8% sodium sulfate solution as in Example 1 results in addition to virtually immediate Ver Thickening the following viscosity values:

1/173 000 mPa · s; 2.5 / 77,000 mPa · s; 5/42 000 mPa · s.

example 7 Dispersion of 80 wt .-% DIMAPA · HCl and 20 wt .-% acrylamide with 40 wt .-% wS

While cooling is allowed at about 20 ° C to 234 g 25.7 % hydrochloric acid add 258 g of DIMAPA slowly. Add 80 g of acrylamide and 140 g of water as well 0.26 ml of thioglycollic acid, 0.25 g of Trilon® B, 1.25 g TAMAC and 0.3 g ABAH too. With hydrochloric acid pH = 7.0 and forms with 20 g sorbitan monoisostearate in 235 g of isohexadecane the emulsion obtained according to Homogeni having 2800 mPa · s at 20 ° C. After removal of the oxygen by blowing out with nitrogen with 5 mg of tert-butyl hydroperoxide and 10 mg of sulfur dioxide catalysed oxide, wherein after 90 min. Spit temperature of 79 ° C sets. After 1 h you cool and activated with 20 g of nonylphenol-6-AeO and 10 g Nonylphenol-9-EO.

The test in 0.8% sodium sulfate solution as in Example 1 results in addition to virtually immediate Ver Thickening the following viscosity values:

1/103 000 mPa · s; 2.5 / 47,000 mPa · s; 5/26 000 mPa · s.

example 8 Dispersion of 83 wt .-% TEMAPA · CH₃Cl and 17 wt .-% acrylamide with 47 wt .-% wS

Dissolve 388 g of TEMAPA · CH₃Cl and 80 g of acrylamide 240 g of water and add 0.26 ml of thioglycolic acid, 0.25 g Trilon® B, 1.25 g TAMAC and 0.3 g ABAH. Man poses adjust the pH to 5.0 with hydrochloric acid and pour the Solution with stirring in a solution of 20 g sorbi tanmonoisostearate in 235 g isohexadecane. After Homoge nize to a viscosity of 3800 mPa · s at 20 ° C. The oxygen is removed and tert-butyl with 5 mg hydroperoxide and 10 mg of sulfur dioxide the Polymerisa started. After 60 minutes is a Spitzenentempera temperature of 89 ° C, after another 60 min cooled and activated as in the previous example. Besides virtually immediate thickening in 0.8% by weight Sodium sulfate solution at 20 ° C following Viscosity values measured:

1/212 000 mPa · s; 2.5 / 96,000 mPa · s; 5/54 000 mPa · s.

The following example explains how to use the polymers according to the invention in textile printing pastes for the acramine F printing process described in U.S. Pat Company brochure of Bayer AG "Acramin-F-Verfahren", revised version of the customer letter Le 378, Sept. 1954, Issue 3.77.

Acramine F = binder
Acrapon A = emulsion thickening made from emulsifier, water and gasoline
Acrafix FH = crosslinker

are registered trademarks of Bayer AG.

example 9

The following printing paste formulations were used (Quantities in g):

Formulation A represents a pure gasoline emulsion. The Thickening is by Acrapon A, which is an emulsion of heavy fuel (boiling range 140 to 200 ° C, aroma tenarm) in water. Recipe B is one Aqueous based formulation with carboxymethylcellulose as a thickener. The formulations C, D, E and F are Formulations with polymers according to the invention.  

Color yield comparison

The color yield of the printing pastes was visually Splits.

thickening Assessment of the color yield Recipe A good color yield Recipe B poor color yield Recipe C better than the gasoline emulsion (A) Recipe D Similar to gasoline emulsion (A) Recipe E Similar to gasoline emulsion (A) Recipe F Similar to gasoline emulsion (A)

handle comparison

To assess the grip in pigment printing is the "finger test" applied.

For this purpose, the fabric is folded. By beta and spread the folded fabric is the handle comparatively determined.

As a reference in the assessment of the prints serves the handle of the gasoline emulsion.

thickening Judgment of the handle Recipe A soft grip that is appropriate for the market Recipe B hard grip Recipe C harder grip than the gasoline emulsion and softer than the carboxymethylcellulose Recipe D slightly harder grip than the gasoline emulsion Recipe E same handle as with petrol emulsion Recipe F Harder grip than (D)

Reibechtheitenvergleich

The printing pastes were based on cotton and BW / PES (50 / 50) and air-dried or 5 min. At 100 ° C. and condensed at 150 ° C for 3 min.

The rubfastnesses were tested according to DIN 54021 and determine the results in the following tables hold.

Recipe A

Recipe B

Recipe C

Recipe D

Recipe E

Recipe F

washfastnesses

The wash fastness were according to the gray scale bewer by comparing how much the origi Prints of washed prints in color fe have changed.

The results were shown in the following tables recorded.

Recipe A

Recipe B

Recipe C

Recipe D

Recipe E

Recipe F

As from the above comparative studies shows, the products according to the invention are the known product based on a gasoline emulsion comparable (color yield, handle, rubbing and washing authenticity). Product B based on an aqueous Thickening agent with carboxylmethyl cellulose are the products according to the invention clearly in terms Color yield and handle with otherwise comparable properties think better.

Claims (14)

1. Water-in-oil dispersions of water-swellable, crosslinked, cationic polymers consisting of

• A) from 30 to 70% by weight of homopolymers or copolymers,
• B) 20 to 50% by weight of a water-immiscible organic liquid,
• C) 0.5 to 10% by weight of a water-in-oil emulsifier,
• D) optionally 0.5 to 10% by weight of a wetting agent,
• E) balance to 100% by weight of water,

characterized in that the homo- or copolymers by polymerization of

• a) 50 to 99.99% by weight of a monomer of the general formula: in the
  R₁ = hydrogen or methyl,
  R₂ and R₃ are hydrogen or alkyl radical having 1 to 4 carbon atoms,
  R₄ and R₅ are alkyl radicals having 1 to 4 carbon atoms,
  X = -NH- and
  n = a number from 0 to 1,
  as salt or in quaternized form,
• b) 0 to 49.99% by weight of comonomers of (meth) acrylamide, (meth) acrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamidomethylpropanesulfonic acid and / or salts thereof,
• c) 0.01 to 5 wt .-% of polyfunctional compounds as crosslinkers

are available. 2. Water-in-oil dispersions according to claim 1, characterized characterized in that as monomers of the general Formula dimethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃ = H; R₄, R₅ = CH₃) and / or tetramethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃, R₄, R₅ = CH₃) used become. 3. W / O dispersions according to claims 1 and 2, characterized characterized in that the monomers of the general Formula neutralized with mineral acids or quater are defined. 4. W / O dispersions according to claims 1 to 3, characterized characterized in that as a crosslinker polyfunctional, ethylenically unsaturated compounds and / or more functional epoxides are used. 5. W / O dispersions according to claims 1 to 4, characterized characterized in that they by reversed-phase emulsions be prepared polymerization. 6. W / O dispersions according to claims 1 to 5, characterized characterized in that they participate after the polymerization be drained or completely drained. 7. W / O dispersions according to claims 1 to 6, characterized characterized in that they have a wetting agent for easy Ren introduced into water is added. 8. Use of the W / O dispersions according to claims 1 to 7 for thickening water and aqueous solutions. 9. Use of W / O dispersions of wasserquellba ren, crosslinked, cationic polymers consisting of

• A) from 30 to 70% by weight of homopolymers or copolymers,
• B) 20 to 50% by weight of a water-immiscible organic liquid,
• C) 0.5 to 10% by weight of a water-in-oil emulsifier,
• D) optionally 0.5 to 10% by weight of a wetting agent,
• E) balance to 100% by weight of water,

wherein the homo- or copolymers by polymerization

• a) 50 to 99.99% by weight of a monomer of the general formula: in the
  R₁ = hydrogen or methyl,
  R₂ and R₃ are hydrogen or alkyl radical having 1 to 4 carbon atoms,
  R₄ and R₅ are alkyl radicals having 1 to 4 carbon atoms,
  X = -NH- or -O- and
  n = a number from 0 to 1,
  as salt or in quaternized form,
• b) 0 to 49.99% by weight of comonomers of (meth) acrylamide, (meth) acrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamidomethylpropanesulfonic acid and / or salts thereof,
• c) 0.01 to 5 wt .-% of polyfunctional compounds as crosslinkers

are available for the production of printing pastes for the textile printing. 10. Use of the W / O dispersions according to claim 9, characterized in that for their preparation as Monomers of the general formula dimethylaminoethyl (meth) acrylate (R₁ = H, CH₃; X = -O-; n = 0; R₂, R₃ = H; R₄, R₅ = CH₃), dimethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃ = H; R₄, R₅ = CH₃) tetramethylaminopropyl (meth) acrylate (R₁ = H, CH₃; X = -O-; n = 1; R₂, R₃, R₄, R₅ = CH₃), and / or Tetramethylaminopropyl (meth) acrylamide (R₁ = H, CH₃; X = -NH-; n = 1; R₂, R₃, R₄, R₅ = CH₃) used become.